A structural study of biocompatible magnetic nanofluid with synchrotron radiation-based X-ray scattering techniques

In this paper, water colloidal solutions of nanoparticles of magnetite (magnetic nanofluids, (MNFs)) are investigated by synchrotron X-ray diffraction (XRD) and small-angle scattering (SAXS). To prevent aggregation, nanoparticles are coated with polyacrylic acid (PAA) in a single solution and citric (CA) in the other solutions. In both cases, the maxima of the particle size distribution from SAXS (9?C10 nm) correspond to the sizes of the magnetite crystallites that were estimated from the broadening of the diffraction lines. In addition, the SAXS data indicate the presence of a significant proportion of aggregates (up to 60 nm in diameter) in both colloidal solutions, although fundamental differences in the structures of aggregates between the MNFs stabilized by PAA and CA were not observed. In this study determination of the structural characteristics of MNFs were carried out in order to obtain stable dispersive non-aggregating nanoparticles of magnetite for use as contrast agents in magnetic resonance tomography, drug carriers, and other biomedical applications.     

Kinetics of colloidal fractal aggregation by differential dynamic microscopy

We study the kinetics of an aggregation process induced by adding salt to a stable colloidal suspension of 73 nm (diameter) particles. Despite the subdiffraction size of the colloidal particles, the process is monitored via optical microscopy, which is used here to obtain time-resolved scattering information about the colloidal aggregates. The radius of the aggregates is determined as a function of time and their fractal dimension is extracted. Our results are compatible with a diffusion limited aggregation process, as independently confirmed by spectral turbidimetry measurements on the same sample.     

光散射聚集速率测定中T矩阵方法的应用

聚集速率是评估胶体体系特性及稳定性的关键参数, 静态光散射和动态光散射则是测量聚集速率的两个重要方法. 然而, 用静态光散射和动态光散射测量聚集速率时, 需要知道有关单粒子和双粒子聚集体光散射特性的数据. 为此, 通常需要把动、静两种方法结合, 才能消去这个数据. 以前各种近似理论曾用来解决这个问题, 但因粒子尺寸和形状的限制, 结果并不理想. 而T矩阵方法可以不受粒子大小和形状的限制计算其光散射特性. 本工作用T矩阵方法直接计算静态光散射和动态光散射所必须的粒子散射特性, 并将该法得到的聚集速率与动静态光散射结合法得到的聚集速率进行了比较, 两者结果很接近. 本工作为简化静态光散射和动态光散射测量聚集速率, 扩展其应用范围开辟了新途径. 关键词： T矩阵')" href="#">T矩阵 光散射法 聚集速率     

Small-angle neutron scattering from micellar solutions

Micellar solutions are the suspension of the colloidal aggregates of the sur-factant molecules in aqueous solutions. The structure (shape and size) and the interaction of these aggregates, referred to as micelles, depend on the molecular architecture of the surfactant molecule, presence of additives and the solution conditions such as temperature, concentration etc. This paper gives the usefulness of small-angle neutron scattering to the study of micellar solutions with some of our recent results.     

Light scattering from colloids

This paper presents a review of light scattering results on static and dynamic properties of ordered colloidal suspensions of charged polystyrene particles and fractal colloidal aggregates. Our studies on static structure factor,S(Q), of ordered monodisperse colloidal suspensions and binary mixtures of particles with different particle diameters, measured by angle-resolved Rayleigh scattering will be discussed. This will include determination of bulk modulus using gravitational compression and observation of colloidal glass (inferred from splitting of the second peak inS(Q)). Dynamic light scattering, with real time analysis of scattered intensity fluctuations, is used to get information about Brownian dynamics of the particles. Recent advances in the field of light scattering from colloidal aggregates which show fractal geometry will also be discussed.     

Dielectrophoretically Modulated Optical Spectroscopy of Colloidal Nanoparticle Solutions in Microfluidic Channels

Optical spectroscopic techniques (e.g., extinction, scattering, and fluorescence spectroscopies) are important for the analysis of colloidal solutions of nanoparticles (NPs). They are routinely applied to plasmonic and quantum-dot NP samples assuming that these contain a single population of particles with modest size and shape dispersity. However, these spectroscopic techniques become less effective when the sample is a mixture of particles with different sizes, shapes, or composition. Here, an original microfluidic method is proposed for the optical spectroscopic analysis of colloidal NP solutions that combines periodic trapping of NPs by dielectrophoresis (DEP) with in situ optical extinction spectroscopy. The periodic trapping leads to modulation of the continuously monitored optical spectrum depending on the DEP properties of the NPs. DEP-modulated spectroscopy is demonstrated using colloidal gold NPs as small as 40 nm diameter. It is found that the DEP modulation is significantly enhanced when employing suitable microfluidic flow over a multielectrode array. Finally, it is shown that the method can identify and characterize the NP species simultaneously present in a mixture of 40 and 80 nm gold NPs, opening the way toward optical spectroscopic analysis of higher complexity NP mixtures through the combination of the DEP-modulated spectroscopy with chemometric methods.     

Particle Manipulation by Ultrasonic Standing Wave Fields to complement dynamic light scattering experiments

Dynamic light scattering is a widely used technique for the sizing of colloidal suspensions. It is capable of measuring particles across the size range from approximately 1 nm to several microns. However the larger particle sizes tend to pose problems for the interpretation of the scattered light signal either by virtue of their light scattering efficiency relative to the smaller species present or the departure of the scattered light signal from Gaussian statistics. Rapid removal of such particles in-situ could extend the use of dynamic light scattering particularly in on-line analysis or laboratory automated measurement. In this paper a method is demonstrated for the in-situ removal of larger particles in suspension by means of ultrasonic standing waves and concurrent dynamic light scattering measurement. The theory behind ultrasonic particle manipulation and its effect on the motion of the particles is discussed. Data from a scattering cell designed to incorporate the ultrasonic technology is presented showing that dynamic light scattering measurements may be carried out under such conditions. Varying the energy density of the ultrasonic field allows particles greater than a defined cut-off diameter to be removed from the measurement region. Theory shows that the minimum cut-off size may be as small as 100 nm. Results presented here demonstrate complete removal at a lower diameter threshold of approximately 2000 nm.     

Helical Structure of Nucleation in a Solution of a Chiral Trifluoroacetylated Amino Alcohol

The occurrence of a nanoscale disperse phase in the homochiral solutions of N-trifluoroacetylated α-amino alcohols (TFAAAs) was found experimentally by the observation of the Tyndall effect and dynamic light scattering (DLS) measurements. The nanoscale fraction was observed at concentrations lower than the critical concentration of gelation and string formation (c*). Direct optical microscopy showed that, as a rule, strings with a helical structure resulted from the homogeneous nucleations. Chirooptical measurements revealed some signs of helicity below the concentration threshold (c*). The molecular dynamics simulation of the condensation of a homochiral TFAAA in heptane showed that TFAAA molecular aggregates 2–3 nm in diameter were formed already after 100 ns. These aggregates have some signs of the homogeneous nucleations with a helical structure, and they can be considered as the nuclei of helical strings.     

Influence of the degree if dispersion of uranine in solutions on the fluorescence light intensity

From scattering measurements of light which does not excite fluorescence, it is found that acetone, dioxan or ethanol in low concentrations reduce the aggregates in an aqueous solution of uranine. In contrast, concentrated solutions of acetone, dioxan and ethanol enhance these aggregates. A correlation is found between the intensity of the light scattered by the aggregates and the fluorescence light intensity.     

Particle Size Characterization of an Extra Fine Milled Product

The present research aims to characterize the particle size distribution of sub micron particles suspended in a liquid. The particles milled are an organic poorly water soluble crystalline product. To characterize the size of these particles, different techniques have been tested: imaging techniques (SEM, CryoTEM), static light scattering techniques, dynamic light scattering techniques, centrifugation and flow field flow fractionation. The results indicate that the studied milled particles have a primary particle size close to 180nm and there is strong evidence of larger particles which are very likely aggregates. This is clearly seen from the Cryo TEM results. All the above mentioned techniques should in principle be able to measure samples of dispersion containing particles of ca 180 nm but several are disturbed by the presence of large aggregates. It is difficult to estimate the amount of aggregate present, but most of the time one is interested in what the primary particle size distribution is. It is clear that no single piece of equipment is capable of exactly determining the particle size distribution of our samples, but the static light scattering with low shear on mixing does give a good representation of what is seen with the image analysis by cryo TEM.     

The Effect of Polydispersity in Primary Particle Size on Measurement of the Fractal Dimension of Aggregates

The use of the mass fractal dimension has become a popular method of characterising the structure of aggregates of fine particles. This parameter is often inferred from scattering experiments that exhibit a power law correlation between scattered intensity and the scattering vector. In this paper we demonstrate deviations from this behaviour that occur when the particles making up the aggregate are not monodisperse, even though the aggregate maintains the same fractal structure as observed in the monodisperse case. We have performed light scattering experiments with aggregating colloidal haematite and performed DLCA computer simulations to explain the observed behaviour. The behaviour can influence the determination of the mass fractal dimension, as can other factors such as scattering effects from primary particles.     

Formation of fractal structures by aggregation of anisometric iron (III) hydroxide particles

Coagulation of anisometric iron (III) hydroxide sols has been studied by dynamic light scattering, TEM and ultra-small-angle X-ray scattering. The anisometry of rod-like individual colloidal particles can be characterised with a mean aspect ratio of 10. It was established for the first time, that the aggregates formed by coagulation of anisometric particles show definite fractal structure with a mass fractal dimension of 1.95 ± 0.05.     

Small-angle neutron and dynamic light scattering study of gelatin coacervates

The state of intermolecular aggregates and that of folded gelatin molecules could be characterized by dynamic laser light and small-angle neutron scattering experiments, which implied spontaneous segregation of particle sizes preceding coacervation, which is a liquid-liquid phase transition phenomenon. Dynamic light scattering (DLS) data analysis revealed two particle sizes until precipitation was reached. The smaller particles having a diameter of ～50 nm (stable nanoparticles prepared by coacervation method) were detected in the supernatant, whereas the inter-molecular aggregates having a diameter of ～400 nm gave rise to coacervation. Small-angle neutron scattering (SANS) experiments revealed that typical mesh size of the networks exist in polymer dense phase (coacervates) [1]. Analysis of the SANS structure factor showed the presence of two length scales associated with this system that were identified as the correlation length or mesh size, ξ = 10.6 Å of the network and the other is the size of inhomogeneities = 21.4 Å. Observations were discussed based on the results obtained from SANS experiments performed in 5% (w/v) gelatin solution at 60°C (ξ = 50 Å, ζ = 113 Å) and 5% (w/v) gel at 28°C (ξ = 47 Å, ζ = 115 Å) in aqueous phase [2] indicating smaller length scales in coacervate as compared to sol and gel.     

不同波长的散射介质后向散射光偏振度特性

基于Stockes矢量,通过测量以线偏振光和圆偏振光入射时脂肪乳剂后向散射光的偏振度,研究了532 nm、650 nm和780 nm三个波长的光与散射粒子粒径为325 nm的脂肪乳剂溶液作用后,其后向散射光的偏振度特性.研究结果表明,对于入射线偏振光,780 nm波长后向散射光中的线偏振光成分多于圆偏振光成分,而532 nm波长则相反;对于入射圆偏振光,三个波长后向散射光中的圆偏振光成分均多于线偏振光成分;532 nm波长的总偏振度高于650 nm和780 nm两个波长各自的总偏振度;线偏振光的保偏性优于圆偏振光的保偏性,但偏振光在散射介质中的穿透深度较小.因此,后向散射成像技术适用于物体表层成像,而且选择波长略大于粒径的线偏振光可以提高成像质量.     

不同波长的散射介质后向散射光偏振度特性

基于Stockes矢量,通过测量以线偏振光和圆偏振光入射时脂肪乳剂后向散射光的偏振度,研究了532nm、650nm和780nm三个波长的光与散射粒子粒径为325nm的脂肪乳剂溶液作用后,其后向散射光的偏振度特性.研究结果表明,对于入射线偏振光,780nm波长后向散射光中的线偏振光成分多于圆偏振光成分,而532nm波长则相反;对于入射圆偏振光,三个波长后向散射光中的圆偏振光成分均多于线偏振光成分;532nm波长的总偏振度高于650nm和780nm两个波长各自的总偏振度;线偏振光的保偏性优于圆偏振光的保偏性,但偏振光在散射介质中的穿透深度较小.因此,后向散射成像技术适用于物体表层成像,而且选择波长略大于粒径的线偏振光可以提高成像质量.     

Change in the intensity of light scattering in a magnetite colloid under the simultaneous action of electric and magnetic fields

The change in the intensity of light scattering in a colloidal solution of magnetite particles in kerosene under the simultaneous action of coaxial and mutually perpendicular electric and magnetic fields has been studied. It has been found that, at certain strengths of mutually perpendicular fields, the change in the scattering intensity is maximal. The effect observed has been interpreted on the basis of the Rayleigh-Debye-Gans anisotropic approximation within the model of orientation of aggregates of magnetite particles under the joint action of the fields.     

Electrooptical properties of aqueous suspensions of nickel hydrosilicate nanotubes

We present the results of our investigations of electrooptical effects that occur as a result of light scattering by an aqueous polydisperse system the disperse phase of which consists of nickel hydrosilicate nanotubes with a chrysotile structure. Multilayer nanotubes were synthesized by the hydrothermal method and had the composition Ni₃Si₂O₅. The dimensions of nanotubes were as follows: the length was 0.1–1 μm or more, the outer diameter was 10–15 nm, and the inner diameter was 3 nm. We have studied relative changes in the intensities of light transmitted and scattered by the suspension that were caused by the orientation of nanotubes in an external electric field. Experiments have been performed at different directions of the linear polarization of the incident and scattered light, different scattering angles, and different degrees of orientation of nanotubes along the field. These measurements allowed us to determine the magnitude of electrooptical effects, such as the conservative dichroism, the light scattering, and the influence of the orientation of nanotubes in the field on the intensity and degree of depolarization of light scattered by them. Curves of free relaxation of electrooptical effects and their field dependences allowed us to determine the distributions of nanotubes and their aggregates in the colloid over lengths and polarizability anisotropy values. The dependences of the degree of depolarization of the scattered radiation on the scattering angle and the relaxation dependences of electrooptical effects allowed us to characterize the aggregation stability of nanotubes in water.     

P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.     

Depolarized light scattering from interacting brownian spheres

The initial decay time of the spectrum and the integrated intensity of depolarized light scattered from a system of interacting spherical and optically isotropic colloidal particles as a function of scattering angle is calculated in the double scattering approximation. These quantities can be reduced in the short-time regime to the static structure factor of single scattering, as observed in polarized scattering for systems of intermediate concentrations of colloidal particles. The results are applied to charged polysterene spheres in solutions and it is shown by numerical calculations that the presence of interactions can modify the angular dependence of initial decay time and integrated intensity considerably.     

Measurement of Aggregate Fractal Dimensions Using Static Light Scattering

Aggregates formed from colloidal particles will vary in shape according to the aggregation regime prevalent. Compact structures are formed when the aggregation is slow, whilst loose tenuous structures are formed when rapid (or diffusion limited) aggregation prevails. These structures can be fractal in nature, that is, there is a relationship between porosity and the number of primary particles making up the aggregate, and is described by the fractal dimension, d_F. Fractal dimensions of hematite aggregates have been measured experimentally using the static light scattering technique. Fractal dimensions varied with aggregation regimes; for the rapid aggregation regime, d_F was found to be 2.8, whilst for conditions in which aggregation was slow (retardation forces prevail), d_F's of 2.3 were measured. For conditions which lead to aggregation in which both diffusion and retardation forces play a part, structures with fractal dimensions such that 2.3 < d_F < 2.8 were found. The effects of adsorbed fulvic acid, a naturally occuring organic acid, on the kinetics of hematite aggregation and on the resulting structure of hematite aggregates were also investigated. The study of aggregate structure shows that the fractal dimensions of hematite aggregates which are partially coated with fulvic acid molecules are higher than those obtained with no adsorbed fulvic acid. The scattering exponents obtained from static light scattering experiments of these aggregates range from 2.83 ± 0.08 to 3.42 ± 0.1. The scattering exponents of greater than 3 indicate that the scattering is the result of objects that contains pores which are bounded by surfaces with a fractal structure, and can be related only to surface fractal dimension. The high fractal dimensions are due to restructuring within the aggregates, which only occured at low coverage by the organic acid.